Atmospheric Chemistry: Fundamental Aspects (Studies in Environmental Science)

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<ul><li><p>Studies in Environmental Science 11 </p><p>Atmospheric Chemistry </p><p>Fundamental Aspects </p></li><li><p>Studies in Environmental Science </p><p>Volume I Atmospheric Pollution 1978 Proceedings of the 13th International Colloquium, held in Pans, April 25-28, 1978 edited by M. M. Benarie </p><p>Volume 2 Air Pollution Reference Measurement Methods and Systems Proceedings of the International Workshop, held in Bilthoven, December 12-16, 1977 edited by T. Schneider, H. W. de Koning and L. J. Brasser </p><p>Volume 3 Biogeochemical Cycling of Mineral-Forming Elements edited by P. A. Trudinger and D. J. Swaine </p><p>Volume 4 Potential Industrial Carcinogens and Mutagens by L. Fishbein </p><p>Volume 5 Industrial Waste Water Management by S. E. Jdrgensen </p><p>Volume 6 Trade and Environment: A Theoretical Enquiry by H. Siebert, J. Eichberger, R. Gronych and R. Pethig </p><p>Volume 'I Field Worker Exposure during Pesticide Application Proceedings of the Fifth International Workshop of the Scientific Committee on Pesticides of the International Association on Occupational Health, held in The Hague, October 9--11, I979 edited by W. F. Tordoir and E. A. H. van Heemstra-Lequin </p><p>Volume 8 Atmospheric Pollution 1980 Proceedings of the 14th International Colloquium, held in Paris, May 5-8, 1980 edited by M. M. Benarie </p><p>Volume 9 Energetics and Technology of Biological Elimination of Wastes Proceedings of the International Colloquium, held in Rome, October 17-19, 1979 edited by G . Milazzo </p><p>Volume 10 Bioengineering, Thermal Physiology and Comfort edited by K. Cena and J. A. Clark </p><p>Volume 1 1 Atmospheric Chemistry. Fundamental Aspects by E. Meszaros </p></li><li><p>Studies in Environmental Science 11 </p><p>Atmospheric Chemistry Fundamental Aspects </p><p>by </p><p>E. Meszaros institute for Atmospheric Physics Budapest, Hungary </p><p>Elsevier Scientific Publishing Company </p><p>Amsterdam Oxford New York 1981 </p></li><li><p>The distribution of this book is being handled by the jollowing publishers: </p><p>for the U.S.A. and Canada Elsevier/NorthTHolland, Inc. 52 Vanderbilt Avenue New York, New York 10017, U.S.A. </p><p>for the East European countries, Peoples Republic of China. Democratic Peoples Republic oj Korea Republic oj Cuba, Socialist Republic of Vietnam, Peoples Republic of Mongolia Akademiai Kiado, The Publishing House of the Hungarian Academy of Sciences, Budapest </p><p>for all remaining areas Elsevier Scientific Publishing Company 335 Jan van Galenstraat P.O. Box 21 1. loo0 AE Amsterdam. The Netherlands </p><p>Ukuy of Coogrem Catrbghg in Pudkatioa Dab </p><p>Mbdros. Ern&amp; Atmospheric Chemistry. </p><p>(Studies in environmental science; v. 11) Rev. and updated translation of A levegdkemia alapjai. Bibliography: p. Includes index. I . Atmospheric chemistry. I . Title. I I . Series </p><p>QC879.6.M4713 551.5 8&amp;204 14 ISBN4444-99753-9 </p><p>ISBN 0-44499753-9 (Vol. 1 1 ) ISBN 0-444-41696X (Series) </p><p>0 Akademiai Kiado, Budapest 1981 </p><p>Joint edition published by Elsevier Sclenllfic Publishing Company. Amslcrdam. The Netherlands and </p><p>Akademidi Kmdo. The Publishing House of Ihe Hungarian Academy d Sc~cnccs. Budnpcst. Hungnry </p><p>All rights reserved. No part of this publication may be reproduced, stored in a retrieval system. or transmitted in any form or by any means, electrical, mechanical, photocopying. recording or otherwise, without the prior written permission of the publishers. </p><p>Printed in Hungnry </p></li><li><p>Hurt not the earth, neither the sea, nor the trees. </p><p>(Revelation 7:3) </p></li><li><p>This Page Intentionally Left Blank</p></li><li><p>Contents </p><p>Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>Chapter I . Introduction . Composition a d strwture of the Earths atmosphere . . . . . . . . . . . . . . . . . 1 . 1 Composition of the air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Structure of the atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>Chapter 2 . Formation and evolution of the Earths atmusphere . Chemistry of main constihats . . . 2 . I Statement of the problem . . . . . . . . . . . . . . . . . 2.2 Dissipation of cosmic gases from the Earths a 2.3 Secondary constituents . . . . . . . . . . . . . . . . . . </p><p>2.5 Increase of the oxygen level during geological times . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6 Variations of CO, level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>2.4 Relation between atmospheric nitrogen and dhe biosphere . . . . . . . . . . . . . . . . </p><p>Chapter 3 . Atmospheric cycle of trace constituents . . . . ...................... 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Hydrogen and helium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>3.2.1 Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.2 Helium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>3.3 Carbon compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. I Methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.2 Carbon monoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.3 Non-methane organic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.4 The atmospheric carb . . . . . . . . . . . . . . . . . </p><p>3.4 Ozone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.1 lntroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.2 Concepts of photochemistry and reaction kinetics ......................... </p><p>3.4.4 The distribution o f t 3.4.3 Formation and destruction of 0, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>3.4.5. Tropospheric ozone ............................... 3.5 Nitrogen compounds . . . . . . . . . . . . . . . . . . . . . . . </p><p>3.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.2 Nitrous oxide . . . . . . . . . . . . . . . . . . . . . . . 3.5.3 Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.4 Nitrogen oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>3.6 Sulfurcompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.2 Origin of atmospheric sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.3 Transformation of sulfur compounds in the atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.4 Concentration of sulfur c ...................... 3.6.5 Atmospheric cycle of sulfur 3.6.6 Atmospheric sulfur cycle ov </p><p>............................. ....................... </p><p>3.7 Summary . . . . . . . . . . . . . . . . . ...................... </p><p>9 </p><p>I I 1 1 14 </p><p>17 17 18 21 22 23 26 </p><p>29 29 31 31 35 35 35 39 42 45 46 46 47 48 55 58 62 62 63 65 69 72 72 72 75 81 85 87 89 </p></li><li><p>8 CONTENTS </p><p>Chapter 4. The atmospheric aerosol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 </p><p>4.1.1 Definition of the aerosol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.2 Classification and measurement of atmospheric aerosol particles 4.1.3 Importance of the study of atmospheric aerosol . . . . . . . . . . . . . . . . . . 96 </p><p>4.2 Origin of atmospheric aerosol particles . . . . . . . . . . . . . . . . . . . . 98 4.2. I Dispersal of particles of surface origin . . . . . . . . 4.2.2 Formation of atmospheric aerosol particles by chemical reaction and condensation. . 99 4.2.3 Other formation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 4.2.4 Comparison of the strength of different aerosol sources . . . . . . . . . . . . . . . . . . . . . . . . . 102 </p><p>4.3 Concentration and size distribution of atmospheric aerosol particles . . . . . . . . . . . . . . . . . . 103 4.3. I Concentration and vertical distrib 4.3.2 The size distribution.. . . . . . . . . . . 4.3.3 Concentration and vertical profile </p><p>4.4.1 The main methods of the identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I I3 4.4.2 Chemical composition of tropospheric aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I I5 4.4.3 Stratospheric particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 </p><p>4.5 Variation of the size of aerosol particles as a function of the relative humidity . . . . . . . . . 128 4.5.1 Theoretical considerations . . . . . . . . . . . . . . . . . . . . . . . . 4.5.2 Results of measurements . . . . . . . . . . . . </p><p>itken particles </p><p>nd giant partic 4.4 Chemical composition of atmospheric aerosol particles . . . . . . </p><p>. . . . . . . . . . . . . </p><p>Chapter 5. Removal of trace substa mosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133 5.2 Dry deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>5.3 Wet deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 5.3. I Rain-out of aer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137 5.3.2 Rain-out of trace gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140 5.3.3 Wash-out of trace constituents below the cloud base . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143 5.3.4 The study of wet remov </p><p>5.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4.2 American measurements . . . . . . . . . . . . . . . . . . . . 152 5.4.3 The Swedish network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 5.4.4 Chemical composition of precipitation waters over the Soviet Union . . . . . . . . . . . . . . 157 5.4.5 Annual variations of the chemical composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 5.4.6 The future of precipitation chemistry measurements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160 </p><p>Chapter 6. Connection of variations of the climate with the chemical Composition of the atinnsphere 161 6.1 lntroductlon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 6.2 Radiation balance of 6.3 The theory of climate and . . . . . . . . . . . . . . . . . . . . . 166 6.4 Present climatic variations . . . . . . . . . . . . . . . . . . . . . 168 6.5 Possible explanation for pr </p><p>the air pollution.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170 </p><p>5.4 Chemical composition of precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </p><p>f climatic variations with </p><p>6.5.1 Variations in the 174 </p><p>6.5.3 Effects of carbon dioxide on the radiation balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179 6.5.2 Effects of tropospheric aerosol particles in the radiation balance . . . . . . . . . . . . . . . . . . </p><p>6.5.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182 </p><p>Subject index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References 183 </p></li><li><p>Preface </p><p>The first version of this book was published in the Hungarian language in 1977. The aim of that edition was to make the elements of air chemistry known to meteorologists, biologists, geochemists and chemists. Until the publication of this book, air chemistry was practically unknown by the Hungarian scientific community except for a very limited group of people. The writer thus wished to summarize its main results and problems in a short and coherent way for those scientists and students who are not familiar with this branch of atmospheric science. </p><p>I t was a pleasant surprise for the author when the Publishing House of the Hungarian Academy of Sciences in Budapest and Elsevier Scientific Publishing Company in Amsterdam decided to publish this book jointly in English. Like the original Hungarian version the present English publication is recommended to those readers who wish to become acquainted relatively easily and quickly from one book with the basic results and concepts on the atmospheric part of the biogeochemical cycle of different constituents. The purpose is thus to summarize, without details, our present knowledge of the concentration, sources and sinks of atmospheric gases and aerosol particles, as well as their physical and chemical transformation in the lower atmosphere (troposphere and stratosphere). Since the chemical composition of the Earth's atmosphere is discussed in relation to atmospheric equilibrium and climate, the content of the book is closely related to environmental sciences. </p><p>Since the preparation of the Hungarian manuscript was finished (beginning of 1975), new, important results have been published in the literature on various problems of air chemistry. For this reason many parts of the original text have been rewritten and enlarged to some extent. Taking into account the great number of publications in this rapidly growing field, the author had to make some selection in the themes and references. Such a selection is strongly subjective. It is hoped, however, that the author's aim to compile the basic elements of air chemistry in a compact way has at least been achieved to a satisfactory degree. </p><p>The English version was reviewed and corrected by Dr. J. P. Lodge (Boulder, Colorado, U.S.A.) who helped the writer to update the manuscript; his kind and invaluable help is gratefully acknowledged. The author is also indebted to Mrs. M. Antal and Mrs. A. Szep (both from Institute for Atmospheric Physics, Budapest, Hungary) who typed the...</p></li></ul>

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